Composition containing 2, 2-bis (2, 3-epoxypropoxyphenyl) propane and trimellitic anhydride



United States Patent 3,400,098 COMPOSITION CONTAINING 2,2-BIS(2,3-EPOXY- PROPOXYPHENYUPROPANE AND TRIMEL- LITIC ANHYDRIDE Harvey L. Parry, ()rinda, Calif., assignor to Shell Oil Company, New York, N.Y., a corporation of Delaware N0 Drawing. Continuation-impart of application Ser. No. 48,856, Aug. 11, 1960. This application June 22, 1964, Ser. No. 377,115

3 Claims. (Cl. 26037) ABSTRACT OF THE DISCLOSURE Novel, particulate compositions of diepoxide and Cluing agents therefore, characterized, i.a., by long shelf life, by high epoxy content and by low viscosity of and relatively long pot life of the melt, comprise free-flowing crystals of 2,2 bis(2,3 -epoxypropoxyphenyl)propane, a curing amount of a stable organic acid anhydride type curing agent which is a solid at 100 F., e.g., trimellitic anhydride, and preferably also a cure accelerator.

This application is a continuation-in-part of US. Ser. No. 48,856, filed Aug. 11, 1960, now US. Patent No. 3,- 159,595.

This invention relates to novel resinifiable compositions containing free-flowing crystals of 2,2-bis(2,3-epoxypropoxyphenyl) propane and solid curing agents, their preparation and their use in preparing epoxy resins.

The novel compositions are particularly useful as adhesives and will be discussed especially with respect to such use. The compositions are, however, adapted to be used also in the preparation of moldings, surface coatings, pottings and other uses to which epoxy resins are conventionally put.

The use of various combinations of epoxy resins and curing agents as adhesives for bonding metals, wood, glass and many other types of surfaces is well known. The epoxy resins which are most widely used for this purpose are the reaction products of 2,2 bis(4 hydroxyphenyl) propane (known as p,p'-bisphenol A) and epichlorohydrin. These products are normally liquid or normal-1y solid materials, depending on the ratio of reactants and the reaction conditions employed in their preparation.

The useas adhesives of the conventional epoxy compounds, 'whether liquid or solid, entails certain disadvantages which are overcome by the compositions of this invention.

When a liquid epoxy resin is used as an adhesive with a quick-acting curing agent it is necessary to mix the curing agent with the resin at most a short time before use because the mixture begins to cure after it is prepared. The time interval during which the mixture remains in liquid, usable condition, the so-ca-lled potlife, is relatively short for such a mixture. If a longer pot life is needed or if a one-package system is desired in which the curing agent has been premixed :by the adhesive manufacturer, then to achieve the necessary package stability a very sluggish curing agent .must be used. This in turn necessitates a long cure at a high temperature, e.g., two hours at 350 F.

When a normally solid epoxy compound is used in an adhesive composition it is generally necessary that it be converted to a liquid before being applied. This requires heating of the solid ep'oxide, generally to a temperature at which curing proceeds so rapidly that only the aforementioned sluggish curing agents can be used. The solid epoxy resins have the further disadvantage of a lower ep-oxide content which gives a less highly crosslinked structure with resultant loss in strength and chemical resistance.

It has also been found that the conventionally used polyepoxy compounds, whether liquids or solids, have undesirably high viscosities at the temperatures at which they are preferably applied. It was, therefore, necessary to devise various special diluents which are used with these compounds in order to reduce the viscosities to desirable levels. Dil-uents for this use must meet special requirements because there is no possibility for inert materials to evaporate when the mixture is used as an adhesive and consequently the diluent must in some manner interreact with the adhesive composition.

It is an object of this invention to provide a particulate composition comprising an epoxy resin and a curing agent which composition is solid at temperatures below about F. and is easily converted to a liquid of relatively low viscosity at temperatures above about F. Another object is to provide such a composition which remains, after being melted, a liquid with a moderately long pot life, suitable for use as an adhesive. It is an object of this invention to provide a solid composite comprising a diepoxide and a curing agent which is characterized by a very long shelf life in its solid state and ability to cure quickly at curing temperatures. Other objects of this invention will appear from the following description thereof.

It has been found that these and other objects of this invention can be accomplished by providing compositions comprising essentially a mixture of free-flowing crystals of 2,2-bis(2,3-epoxypropoxyphenyl)propane (the diglycidyl ether of p,p bisphenol A), a curing amount of a stable curing agent therefor which is a solid at 100 F. and preferably also a cure accelerator.

The compositions prepared according to this invention are particularly useful as adhesives. The preferred compositions are characterized by excellent shelf life. Very mild heating, in most cases heating to between 100 and F. or slightly higher, converts the solid mixtures to liquids. Those compositions comprising heat activated curing agents subsequently remain liquid even when cooled to amuch lower temperature and have a pot life of up to three days. The preferred compositions cure rapidly at curing temperatures; these are generally elevated temperatures of at least about 200 F. A further advantage of the compositions is that they have a high epoxide content relative to other epoxy adhesives and that they are, therefore, adapted to yield exceptionally strong bonds which retain their strength at high temperature.

A substantial practical advantage of compositions prepared according to this invention is that they provide a practical means for furnishing a correctly proportioned mixture of polyepoxide and curing agent which only requires heating to convert it into usable form. This avoids the possibility of proportioning errors in the manufacturing operation which are likely to occur when polyepoxide and curing agent must be mixed at the site of application.

METHODS OF PREPARING BLENDS It has been found that conventional methods are not generally suitable for preparing the compositions of this invention. In order to prepare a useful free-flowing solid composition it is essential that the crystalline diglycidyl ether be at no stage permitted to become liquefied. It is however necessary that the mixtures of the crystalline diglycidyl ether and such curing agents, promoters, fillers and modifiers as are employed be intimate blends of the ingredients, in order that a resin mixture of uniform composition be for-med. Conventional grinding of the dry ingredient usually results in liquefaction of the mixture and does not produce a useful composite.

It has been found that desired blends can be prepared by suspending the ingredients to be blended in a volatile liquid in which the ingredients of the mixture are insoluble, e.g., in isopentane, heptane, isooctane or other volatile naphtha type liquids, and mixing the ingredients in suspension in such liquid in a device such as a ball mill, a vibrating ball mill or a roll mill. After the mixture has been prepared the solvent may be removed by filtering or decanting and remaining solvent removed by evaporation to produce a dry blend.

Suitable suspending liquids must meet these requirements:

(1) They must be non-solvents for the ingredients of the mixture.

(2) They must be inert, i.e., nonreactive towards the ingredients of the mixture.

(3) They must be sufficiently volatile to permit their removal from the blended mixture by evaporations at temperatures below about 100 F. Forced evaporation may be used.

It has been found that nonaromatic hydrocarbon liquids, particularly parafiins having from 5 to 9 carbon atoms per molecule, are very suitable suspending liquids. Parafiinic mixtures containing ingredients of up to 10 or 12 carbon atoms per molecule or containing cycloparaffins are also suitable.

The amount of inherent liquid employed is at least sufficient to produce a suspension which has a consistency of a thick paste. More liquid may be added, sutficient to produce a suspension which is a relatively fluid paste or slurry. From 15 to parts of liquid per 100 parts solid ingredients is generally a preferred ratio. As little as 5 or 10 parts or as much as 50 or 100 parts may sometimes be used.

Dry blending methods in which no pressure is applied to the mixed components may be employed, e.g., the various components may be mixed in a fluidized solids system.

COMPONENTS USED IN THE COMPOSITIONS The epoxzd'e.The reaction of epichlorohydrin with 2,2-bis(4-hydroxyphenyl)propane to produce a complex mixture of polyglycidyl ethers is well-known. It is described in some detail, for example, in US. 2,467,171 to Werner et al. and in US. 2,651,589 to Shokal et al. The simplest addition product which is formed in this reaction is the 2:1 addition product, 2,2-bis(2,3-epoxypropoxyphenyl)propane which is represented by the formula The higher molecular addition products which are also formed in the reaction have the general formula wherein n is an integer and R represents the divalent hydrocarbon radical of the bisphenol. By appropriate control of the ratio of epichlorohydrin to bisphenol in the reaction and of other conditions, complex mixtures can be produced which contain a relatively high proportion of the digylcidyl ether, e.g., 70%90% by Weight or more of the total reaction product, the remainder being mainly higher addition products. Similarly, solid polyepoxy polyethers of higher molecular weight can be prepared by appropriate control of ratios and reaction conditions.

It has been found that by careful preparation of a concentrate containing a relatively high proportion of the diglycidyl ether and by careful crystallization of the diglycidyl ether from a suitable solvent mixture it is possible to recover the diglycidyl ether, 2,2-bis(2,3-epoxypropoxyphenyDpropane, in the form of free-flowing crystals of substantially 100% purity. Following are representative properties of the crystalline compound prepared in this manner, compared with such properties for a typical commercial liquid polyepoxide containing about of the diglycidyl ether and for two typical commercial polyglycidyl ethers of the same type which are normally solids.

X Sharp melting point, typical of pure compound. 2 Durrans mercury method. 3 supercooled liquid.

The melting point of the crystalline diglycidyl ether may vary slightly in batches of different purity. It is in the range between and 113 F. It is a distinct, clear melting point in contrast to the softening points exhibited by solid polyglycidyl ethers of higher molecular weight.

It may sometimes be desirable to admix a conventional solid polyepoxide with the crystalline diglycidyl ether of p,p'-bisphenol A in preparing the powdered composite of this invention. In such admixtures, up to 25 parts of conventional solid polyepoxide to 100 parts of crystalline diglycidyl ether of p,p'-bisphenol A may be employed. The solid polyepoxide may be, for example, that mentioned in US. 2,633,458 to Shokal as Polyether E, having a Durrans melting point of 98 C. and molecular weight of 1400, or that having a softening point of 131 C. and a molecular weight of 2900, or other similar normally solid polyepoxides. In general, superior results are obtained from composites containing the diglycidyl ether of p,p'- bisphenol A as the sole epoxide component.

Curing agents.As essential requirement of all curing agents suitable for use in this invention is that they be solids at ambient temperatures, i.e., up to about 100 F. Their melting points should preferably be above 100 F. In the following discussions of curing agents the requirement that they be solids at ambient temperatures is not always repeated but will be understood.

Not all solid curing agents are equally useful. In general it is desirable that the curing agent be relatively fast acting, once the mixture of resin and curing agent has been melted and heated to a curing temperature. The rate at which they act is known for most curing agents or can be readily determined.

It has also been found that some solid curing agents interreact with crystalline 2,2-bis(2,3-epoxypropoxyphenyl) propane in such a way that the solid mixture gradually, and spontaneously, liquefies and then begins to cure at a relatively rapid rate. It appears that this spontaneous reaction takes place with curing agents whose vapor pressure is relatively high at ambient temperatures. These are, in general, compounds with relatively low melting points, e.g., below 200 F. The effect has sometimes been observed, for example, with metaphenylene diamine (M.P. F.), methylene dianiline (M.P. F.) and with hexahydrophthalic anhydride (M.P. 9597 F). Similarly, solid complexes of BF;, which have a relatively high vapor pressure of B1 associated with the complex at ambient temperatures may result in liquefaction of the mixture. Mixtures prepared with such curing agents are nevertheless useful, e.g., where it is convenient to store the mixture under refrigerated conditions or Where the advantages of convenient mixing of solids are desired and the mixtures are to be used without extended storage.

A preferred group of curing agents are the anhydrides of polycarboxylic acids. They are preferably used with activators or promoters of the type to be described hereinafter. The use of dicarboxylic acids for curing epoxy resins is discussed in US. 2,324,483 to Castan. Various modifications, particularly with reference to use of prometers, are described in US. 2,768,153 to Shokal, US. 2,839,495 to Carey and Swiss 273,405.

A particularly preferred group of curing agents are those compounds having at least one cyclic anhydride group, i.e.,

O V at and a free carboxyl group which is not more than 3 carbon atoms removed from the anhydride group, the carbon atoms of the anhydride and the carboxyl groups not being included in the count. These anhydride compounds may be aliphatic, cycloaliphatic or aromatic and may be saturated or unsaturated. Examples of these compounds include, among others, trimellitie anhydride, 1,2,3-(6-methyl 4 cyclohexene)tricarboxylic 1,2-anhydride, 1,2,4-butane tricarboxylic 1,2-anhydride, 1,2,3-pentane tricarboxylic 1,2-anhydride, 1,2,4-hexane tricarboxylic 1,2-anhydride and 1,2,5-(3-chloroheptane)tricarboxylic 1,2-anhydride. Other examples include the half esters, halides and amides of pyromellitic anhydride such as the monobutyl ester Other examples are adducts made from 2 moles of pyromellitic dianhydride and 1 mole of a glycol, e.g.,

(I) 0 0 o ii-o-iv-o-th" \C -o 0 0H 0 0 OH C/ Other suitable anhydrides are the normally solid aliphatic, cycloaliphatic and aromatic monoand dianhydrides and their chlorinated derivatives. Examples of these anhydrides include, among others, phthalic anhydride, isophthalic anhydride, diand tetrahydrophthalic anhydrid succinic anhydride, maleic anhydride, pyromellitic dianhydride, stearic anhydride, monochloromaleic anhydride, tetramethylsuccinic acid anhydride, glutaric acid anhydride, a,a,' -trimethyl glutaric acid anhydride, app-trimethyl glutaric acid anhydride, suberic acid anhydride, azelaic acid anhydride, sebacic acid anhydride, itaconic acid anhydride, u-methyl itaconic acid anhydride, 6-ethyl- 4-cyclohexadiene-1,2-dicarboxylic acid anhydride, 3,6-dimethyl-4-cyclohexadiene-1,2-dicarboxylic acid anhydride, 6 butyl 3,5-cyclohexadiene-1,2-dicarboxylic acid anhydride, 3-methoxy-1,2,3,o-tetrahydrophthalic acid anhydride, 3-butoxy-1,2,3,G-tetrahydrophthalic acid anhydride, polyadipic acid anhydride, 'polysebacic acid anhydride, 3,4,5,6,7,7 hexachlorO- 3,6-endomethylene-1,2,4,5-tetrahydrophthalic anhydride (chlorendie anhydride), and the like and mixtures thereof provided the mixtures are solids at ambient temperature.

Basic promoters for acid imhydrides-It is known that the cure of polyepoxides by means of acid anhydride curing agents is generally relatively slow unless a promoter is added. Preferred promoters are basic compounds. A particularly suitable promoter is dicyandiamide. Other suitable promoters are the organic substituted phosphines,

arsines, stibines and bismuthines as described in U.S. 2,768,153 of Shokal, e.g., triphenylphosphine and the like.

Other suitable promoters for acid anhydrides as curing agents are solid BF complexes with various bases such as the complexes described in US. 2,717,885 to- Greenlee. Suitable solid complexes of BF are, for example, those with aniline, dimethylaniline, triethylamine, trimethylamine, dirnethylbenzylamine, tripropylamine, lauryl amine, diethyl ether and ammonia, phenyl hydrazine, diethy ether and diethyl triamine, diaethyl ether and mono-nbutyl amine, amyl amineand ether, decyl amine and ether, morpholine and ether, benzyl aniline and ether and pyridine and ether.

FilIers.A variety of inert solid compounds are known to be useful as so-called fillers in epoxy resin composi tions. These compounds are added to provide various desired characteristics, e.g., an increase in density or a different appearance of the finished resin or alteration of the rheological characteristics of the adhesive in the paste form. Conventional solid fillers are suitably applied in the compositions prepared according to this invention. They include, for example, powdered metals such as aluminum powder, and other finely divided materials such as asbestos, various clays, and the like.

M0difiers.-It is common practice in the industry to add minor amounts of various thermoplastic resins to epoxy resin compositions to decrease their brittleness. Such materials are suitably added to the compositions according to this invention. They include, for example, polyvinyl formal, polyvinyl chloride,, polyvinyl acetate, and polyacrylamide.

Other conventional modifiers of epoxy resins may be usedif they are solid at ambient temperatures.

'PROPORTIONS OF INGREDIENTS In referring to the amount of an ingredient of a resin composition, the conventional measurement is in parts by weight per parts of resin, abbreviated phr. In the following, phr. refers to parts by weight per 100 parts of 2,2-bis(2,3-epoxypropoxyphenyl)propane.

Solid polyepoxypolyethers may be admixed in concentrations up to 25 phr. They are preferably omitted altogether or used in low concentrations, e.g., up to 10 phr.

The proportions of various curing agents required to cure a polyepoxide are known to the art and can be found in textbooks and industrial publications. Thus, a curing amount of a curing agent has a definite meaning to the worker skilled in this art. Following is a brief rsum:

Acid anhydride curing agents are preferably employed in approximately stoichiometrically equivalent proportions. As used herein in relation to the amount of curing agent and polyepoxide, the expression equivalent amount refers to that amount of anhydride needed to furnish one anhydride group for every epoxy group in the polyepoxide to be cured. Although satisfactory cures are obtained by using at least 0.8 equivalent of the anhy: dride, for best results such curing agent should be employed in approximately the equivalent amount. Curing agent to epoxide equivalent ratios of 0.85:1 to 1.15:1 are suitably employed.

The activator for an anhydride curing agent, i.e., dicyandiamide or BF -amine complex or the like, is needed only in a very small amount. Excellent results are obtained when the activator is utilized in amounts varying from 0.01 to 10 phr. and preferably in amounts varying from 0.1 to 2 phr.

The amount of filler which can be employed is a function of the physical properties of the filler and of the desired characteristics of the finished products. Thus, finely divided aluminum dust can be employed in concentrations as high as 200 phr. Its use in concentrations of up to 100 phr. is particularly preferred. Other fillers are generally used in much lower concentration, e.g., in the range from 10 to 50 phr., because of their lower density. For example, asbestos dust may be suitably employed in concentrations up to 40 phr. When fillers are employed, the amount usually exceeds phr.

Thermoplastic resins, added to decrease brittleness, are useful in the concentration range of l to 100 phr., and are preferably used in concentrations from 10 to 50 phr.

METHODS OF APPLICATION A typical composition prepared according to the present invention is a free-flowing powder which melts between 100 and 120 F. The melt does not resolidify when cooled to room temperature. The powder has a shelf life of at least six months when stored between 32 and 40 F. when the curing agent is of the heat activated type. When stored at ambient temperature there is a slow interreaction between the polyepoxide and curing agent, resulting in a gradual increase of the viscosity of the composition when melted.

The powder composites of the invention are particularly suitable for use as adhesives. They can be used to cause adhesion between a wide variety of different materials. It is well known to the art what materials can be bonded by polyepoxide adhesives. Typical bondable materials are metals, such as aluminum, beryllium, brass, copper, iron, steel, titanium and others; inorganic nonmetals such as masonry materials and glass; and organic solids such as thermoset polymers and rubbers. In general the surfaces of the materials to be held together by the adhesive are cleaned in a well known manner. Certain organic materials, particularly thermoplastics, require special surface treatments which are known to the art.

The powder composite, when it is to be used as an adhesive, may be applied, for example, in the following two ways:

(1) As an even layer of powder, which may be followed by heating to sinter the mixture sufiiciently to hold it in place. The physical method of applying the adhesive powder to a material to be bonded provides no special problems. The material may be applied manually, or conventional powder handling equipment may be employed. It is only necessary to avoid heating the powder at any point above a temperature of about 100 F. to avoid causing it to liquefy.

(2) By melting the composite in a separate container by mild heating and applying a thin even layer of the resulting paste.

The parts are then assembled and held together with clamps or by other means. The composites of this invention generally require curing temperatures of about 200 F. or higher. Typical conditions are from /2 to 3 hours at 250 F., from A to 1 hour at 300 F. and from 2 to minutes at up to 500 F.

In any particular instance a suitable curing time and temperature can be determined by a brief study of the effect these conditions have on the tensile strength of the bond between particular materials to be bonded. In general, as the curing time at a given temperature is increased a maximum bond strength is obtained at some particular time within the above stated ranges. The use of higher temperatures results in decreasing the amount of time required to obtain the strongest bond.

EXAMPLES The invention will be illustrated by means of the following examples. It will be understood that these examples are for the purpose of illustration only and the invention is not to be limited thereby but only by the appended claims. Unless otherwise indicated, parts are parts by weight.

Example 1 A composite was prepared having the following composition.

8 Component: Parts Crystalline 2,2 bis(2,3-epoxypropoxyphenyl) propane Trimellitic anhydride 55 Dicyandiamide 0.5 Asbestos floats 40 In preparing the composite, the weighed dry ingredients were placed into a vessel and a sufficient amount of isooctane added to give a suspension which had the appearance of a stiff, grainy paste. This paste was then passed through a three roll paint mill several times, care being taken to avoid build-up of frictional heat to a level at which all of the solvent would have been removed by vaporization. The paste was then spread out to dry at room temperature and the resulting dry free-flowing powder placed in a container and stored in a cool place.

Equally good mixing was obtained by use of a two roll plastic mill in place of the paint mill.

Example 2 Composites were prepared having the same formulation as the composite of Example 1 but employing somewhat different mixing techniques. The weighed dried ingredients were placed into suitable containers and sufiicient isopentane added to make a suspension which had the appearance of a fluid grainy paste. Steel balls were then placed into the containers and the containers tightly closed and agitated, such as by rolling on a bottle roller or shaking in a paint shaker, until good blending had been obtained. Several hours on the bottle roller or 5 to 15 minutes in a paint shaker were sufficient. The pastes were removed from the containers, spread out in a thin layer and dried at ambient temperature. The resulting dry, free-flowing powders were stored in a cool place.

Example 3 The procedures of Examples 1 and 2 are repeated, substituting each of the following liquids for the isooctane and isopentane, respectively: V.M. & P. naphtha (an aliphatic naphtha boiling in the C -C range and containing about 15% aromatics); a highly aliphatic naphtha consisting largely of the heptane cut; and aliphatic naphtha consisting largely of the hexane cut; and a white gasoline. The use of each of these liquids results in a satisfactory operation. It is preferred, however, to usethe slightly higher boiling materials, e.g., the C or C cut or the gasoline in the method of Example 1 and the lower boiling, such as isopentane, hexanes or heptanes, in the method of Example 2.

Example 4 A portion of the powdered composite prepared according to Example 1 is heated to about F. The powder melts, resulting in a moderately thick paste of uniform composition. This paste is sufficiently thixotropic so that it can be applied to a vertical surface without running, even during cure at elevated temperature. The paste is relatively viscous at room temperature. It is still a useful adhesive after storage for two to three days at 80 F. or storage of about 1 day at 120 F.

Portions of the paste are heated to a temperature in the range between 110 and F. and used to bond together two sheets of etched aluminum, utilizing a variety of curing temperatures and times. The sample sheets of aluminum are bonded by spreading adhesive over about a A-inch width along an edge of each sheet and then placing the two sheets together with a /2-inch overlap, clamping them together and placing the assembly in a preheated oven provided with forced air circulation for the desired length of time. The sheets are sawed into strips in which the area of overlap is normally about /2 x 1 inch. The strips are then tested in tension at the desired test tempera ture at a loading rate of 1400 p.s.i. per minute.

The procedure of Example 4 is repeated with solvent wiped steel substituted for the aluminum sheet. The tensile shear strengths obtained are approximately 10% lower than the values found with aluminum in Example 4.

Samples of brass sheet, copper sheet and titanium sheet are similarly satisfactorily bonded by the adhesives of Examples 1, 2 and 3.

Satisfactory bonds are also obtained with the composites of Examples 1, 2 and 3 between brick, concrete, glass, polystyrene, phenol formaldehyde plastics, rubber, wood and paper.

Satisfactory composites are prepared by bonding sheets of fibrous materials such as fiber glass with the composites of these examples in the same manner in which such compositions are prepared from other polyepoxide resins.

Example 6 A composite is prepared similar to Example 1, utilizing a crystalline 2,2 bis(2,3-epoxypropoxyphenyl) propane having an equivalent weight of 173 per epoxy group. Varying the amount of trimellitic anhydride from 55 to 6'5 phr. and utilizing a fixed curing cycle results in a systematic variation of the tensile strength of the resulting bond through a range of 20%, the maximum being obtained at about 62 phr. of trimellitic anhydride.

Varying the amount of dicyandiamide accelerator in the composition having 60 phr. of the trimellitic anhydride results in about 17% variation in tensile strength, the strength of the bond decreasing as the amount of accelerator is increased.

Example 7 Compositions are prepared according to Examples 1, 2 and 3 but substituting pyromellitic dianhydride in stoichiometric quantity for the trimellitic anhydride. The resulting powder composite is used as an adhesive in accordance with Examples 4 and 5. Satisfactory bonds are obtained.

Example 8 In Examples 1 to 3, 0.1 phr. and 1 phr., respectively, of benzyl diamethylamine are substituted for the dicyandiamide. The resulting composites are employed as adhesives with satisfactory results.

Example 9 In Examples 1 to 3, 0.1 phr. and 1 phr., respectively, of benzyl dimethylamine are substituted for the dicyandiamide. The resulting composites are employed as adhesives with satisfactory results.

Example 10 For the asbestos floats of Examples 1 to 3 there are substituted a similar amount of each of the following fillers: silica, finely divided aluminum, calcium carbonate, wollastonite, mica, titanium dioxide and carbon black. Satisfactory adhesion is obtained with each of the resulting composites.

Example 11 The formulation of Example 1 is modified by adding 15 to 30 phr., respectively, of polyvinyl formal. Upon melting prior to application, the resulting liquid phase is tackier and upon cure the resulting bond has improved flexibility.

Example 12 Polyvinyl chloride is substituted for the polyvinyl formal in Example 11 with similar results of improved tack and flexibility.

Example 13 A partially hydrolyzed acetate is substituted for the polyvinyl formal of Example 11 with similar results of improved tack and flexibility.

Example 14 A polyacrylamide is substituted for the polyvinyl formal of Example 11 with similar results of improved tack and flexibility.

I claim as my invention:

1. A solid, particulate composition essentially comprising free-flowing crystals of 2,2-bis(2,3-ep0xypropoxyphenyl)propane, from 0.85 to 1.15 stoichiometric equivalents of trimellitic anhydride and from 0.01 to 10 phr. of dicyandiamide.

2. A solid, particulate composition essentially comprising free-flowing crystals of 2,2-bis(2,3-epoxypropoxyphenyl) propane and from 0.85 to 1.15 stoichiometric equivalents of trimellitic anhydride.

3. A composition according to claim 2, which contains from 0.01 to 10 phr. of dicyandiamide and from 10 to 200 phr. of an inert solid filler.

References Cited UNITED STATES PATENTS 1/ 1960 Bruin et al 26047 6/1963 Smith et al. 26047 

